CN102134720A - Method for surface treating a heat exchanger, surface treatment agent, and aluminum heat exchanger - Google Patents
Method for surface treating a heat exchanger, surface treatment agent, and aluminum heat exchanger Download PDFInfo
- Publication number
- CN102134720A CN102134720A CN201110025255XA CN201110025255A CN102134720A CN 102134720 A CN102134720 A CN 102134720A CN 201110025255X A CN201110025255X A CN 201110025255XA CN 201110025255 A CN201110025255 A CN 201110025255A CN 102134720 A CN102134720 A CN 102134720A
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- CN
- China
- Prior art keywords
- heat exchanger
- surface treatment
- treatment agent
- mentioned
- vinyl alcohol
- Prior art date
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- 239000011241 protective layer Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 229940048462 zinc phosphide Drugs 0.000 description 1
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/089—Coatings, claddings or bonding layers made from metals or metal alloys
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/04—Tubular or hollow articles
- B23K2101/14—Heat exchangers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2275/00—Fastening; Joining
- F28F2275/04—Fastening; Joining by brazing
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Air-Conditioning For Vehicles (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
A method for surface treating a heat exchanger and an aluminum heat exchanger obtained from this method are provided that can effectively suppress the foul odor characteristic to flux that emanates following degradation of a hydrophilic coating film and a chemical conversion coating film in a non-corrosive flux brazed heat exchanger on which flux easily remains. The method for surface treating a non-corrosive flux brazed heat exchanger made of an aluminum material conducts a pickling treatment step, a chemical conversion treatment step, and a deodorizing treatment step on the heat exchanger, in which the acidic cleaning agent contains nitric acid and sulfuric acid as well as a predetermined amount of ferric salt, and the surface treatment agent contains silica grains coated by a vinyl alcohol polymer and polyallylamine resin such that the total content of the silica grains and the vinyl alcohol polymer is a predetermined amount.
Description
Technical field
The present invention relates to surface treatment method, surface treatment agent and the aluminum-made heat exchanger of heat exchanger.
Background technology
The complex structure of the heat exchanger part of air-conditioning plant and the heat exchanger part of air purifier promptly, remains on aluminium radiator fin (aluminium fin) between aluminum tube with narrow and small interval for heat exchanger effectiveness is improved.Therefore, as required, change into processing by surface to aluminium radiator fin after, carry out hydrophilization, thereby make refrigeration time institute's agglomerative water be easy to discharge (for example, with reference to patent documentation 1).
Mostly the radiator element of heat exchanger etc. is that soldering is assembled into by aluminium alloy is carried out.As the method for soldering, can be divided into the method for using solder flux (flux) and the method for not using solder flux.Can enumerate vacuum brazing method (VB method) as the method for not using solder flux, can enumerate non-aggressive solder flux soldering (flux brazing) method (NB method) of using fluorochemical class solder flux as the method for using solder flux, because excellent corrosion resistance, equipment cost are low, gradually adopt the NB method now.But, form slimy solder flux and be attached to method on the heat exchanger because the NB method is a kind of will being dissolved in the water, therefore exist after the soldering solder flux residual and malodorous problem takes place thus.
In order to solve such problem, be necessary to remove residual flux, but adopt the pickling of in the past carrying out as the preceding operation that changes into processing, be difficult to remove fully residual flux.For example, disclose in the patent documentation 2 and a kind of the metallic substance that contains aluminium has been carried out the surface-treated method, promptly, before hydrophilicity-imparting treatment, use contains at least a kind the acidic aqueous solution that is selected from sulfuric acid, hydrofluoric acid, nitric acid and the phosphoric acid and carries out the chemical corrosion processing, use the aqueous solution of zinc phosphide, phosphatization titanium to change into processing afterwards, even but by such surface treatment method, the effect of removing segregation thing such as residual flux is also insufficient.And the processing that changes into after the pickling also is difficult to cover residual flux.
The surface treatment method of heat exchanger as other discloses a kind of changing on the epithelium of forming; formation is by containing the wetting ability of resinous principle (a) with the resultant of reaction of linking agent composition (b); the method of the 2nd protective layer that the hydrophobic resin epithelium is formed; this resinous principle (a) contains water-soluble polymers; this water-soluble polymers has: be selected from primary amino; secondary amino group or uncle's amino; quaternary ammonium group; amide group; carboxyl; sulfonic group; Oxyranyle; the hydrophilic group more than a kind in phosphonate group and the hydroxyl; with be selected from amide group; carboxyl and hydroxyl and with the different types of crosslinking reaction group of the hydrophilic group of above-mentioned selection; this its total amount of linking agent composition (b) surpasses the crosslinked equivalent of resinous principle; and contain (i) 3 valency chromium cpds and (ii) fluorine coordination compound (for example, with reference to patent documentation 3).But this method is not suitable for the heat exchanger that adopts non-aggressive solder flux method for brazing to make.
In addition, disclose a kind ofly in the patent documentation 4, used molysite to carry out pickling and effectively removes after the segregation thing of brazing solder, changed into processing again, carried out the method for hydrophilicity-imparting treatment then.But the employed treatment agent that changes into of such method is that chromate changes into treatment agent, promptly mainly from the viewpoint of the burden of environment is not advised using.
Change into treatment agent as Chrome-free, can enumerate the treatment agent that forms composition with heavy metals such as zirconium, titanium, hafniums as epithelium.But, particularly change into changing in the epithelium that treatment agent obtains at above-mentioned Chrome-frees such as changing into treatment agent by the zirconium class, exist on the heat exchanger after the soldering and can't form the problem that changes into epithelium uniformly, and the adhesivity between the hydrophilic epithelium that is obtained by in the past hydrophilizing agent is insufficient.Therefore, long-term cooling, heat repeatedly and when causing hydrophilic epithelium deterioration, change into also deterioration of epithelium along with the deterioration of hydrophilic epithelium.Therefore, owing to hydrophilic epithelium and change into epithelium generation deterioration heat-exchanger surface is exposed, thereby cause the problem of the distinctive stink of residual flux on heat-exchanger surface.
Particularly in citing document 4, existence is about the record of the odor control additive be made up of the organism that contains amide group and/or phenylol, but this odor control additive is used for suppressing chromate changes into distinctive stink in the chromic salt that treatment agent contains, do not provide any solution to suppress to use Chrome-free to change into treatment agent in the record and change into when handling, because of hydrophilic epithelium, change into the peculiar stink that the deterioration of epithelium causes.
Patent documentation 1: Japanese kokai publication hei 05-302042 communique
Patent documentation 2: Japanese kokai publication hei 11-131254 communique
Patent documentation 3: TOHKEMY 2001-174192 communique
Patent documentation 4: TOHKEMY 2002-30462 communique.
Summary of the invention
In view of the above problems, the object of the invention is the aluminum-made heat exchanger that a kind of surface treatment method of heat exchanger is provided and adopts this method to obtain, this surface treatment method can effectively be suppressed in the non-aggressive solder flux soldering heat exchanger of easy residual flux, along with hydrophilic epithelium, change into the deterioration of epithelium and the distinctive stink of solder flux that produces.
The present invention relates to a kind of surface treatment method of heat exchanger, this surface treatment method comprises: make the non-aggressive solder flux soldering heat exchanger that acid detergent contact made by aluminium cleanup acid treatment operation (1), make the zirconium class change into changing into treatment process (2) and making the surface treatment agent contact change into the deodorization treatment process (3) of the above-mentioned aluminium after the treatment process of above-mentioned aluminium after the treatment agent contact pickling treatment process; Above-mentioned acid detergent contains nitric acid and sulfuric acid, and the molysite that contains 0.01 ~ 5 quality %, above-mentioned surface treatment agent contains silicon dioxide granule and the polyallylamine resin by the vinyl alcohol polymer lining, the above-mentioned silicon dioxide granule that is contained in the above-mentioned surface treatment agent and the total content of above-mentioned vinyl alcohol polymer are 0.2 ~ 25 quality %, and the mass ratio of above-mentioned silicon dioxide granule and above-mentioned vinyl alcohol polymer is 30:70 ~ 70:30.
Above-mentioned molysite is preferably and is selected from least a in ferric sulfate, iron nitrate, iron acetate and the iron(ic) chloride.
The preferred used for automobile air conditioning vaporizer of above-mentioned non-aggressive solder flux soldering heat exchanger.
The present invention relates to a kind of above-mentioned surface treatment agent that is used for the surface treatment method of above-mentioned heat exchanger.
The present invention relates to a kind of aluminum-made heat exchanger that adopts the surface treatment method of above-mentioned heat exchanger and obtain.
The surface treatment method of heat exchanger of the present invention, contain nitric acid and sulfuric acid by making, contact the non-aggressive solder flux soldering heat exchanger of making by aluminium with the acid detergent of the molysite of specified quantitative, and make the zirconium class change into treatment agent to contact with this heat exchanger, make the silicon dioxide granule that contains by the vinyl alcohol polymer lining then, and the surface treatment agent of polyallylamine resin contacts with this heat exchanger, thereby can be on heat-exchanger surface, long term maintenance is brought into play the adhesivity of hydrophilic epithelium, the vinyl alcohol polymer in the above-mentioned surface treatment agent and the total content of silicon dioxide granule, and mass ratio is by being decided in the scope.According to the present invention, can effectively carry out epithelium formation to being attached with the non-aggressive solder flux soldering heat exchanger that causes malodorous solder flux, and deterioration does not take place in epithelium for a long time, therefore the substrate of heat exchanger can not expose, thereby can suppress to remain in the distinctive malodorous generation of solder flux of heat-exchanger surface.
Embodiment
Below the present invention is described in detail.
The present invention a kind ofly gives non-aggressive solder flux soldering heat exchanger good deodorization and hydrophilic surface treatment method.The surface treatment agent that uses in the deodorization treatment process of the present invention contains silicon dioxide granule and the polyallylamine resin by the vinyl alcohol polymer lining.By using above-mentioned containing by the silicon dioxide granule of vinyl alcohol polymer lining and the surface treatment agent of polyallylamine resin, can hide the solder flux that remains on the non-aggressive solder flux soldering heat exchanger for a long time, form and keep the epithelium of stink inhibition and wetting ability excellence.
As long as above-mentioned polyallylamine resin has the represented structure unit of following formula (1), then be not particularly limited.The adhesivity of above-mentioned polyallylamine resin makes the epithelium of possess hydrophilic property that deterioration not take place for a long time.Thus, can hide the residual flux on the heat exchanger, suppress peculiar malodorous generation in the solder flux.
That the polyallylamine resin has is water-soluble, with the characteristics such as consistency excellence of vinyl alcohol polymer.Therefore, compare with the similar structures with amino etc. and other polymkeric substance or the compound of characteristic, the polyallylamine resin that is added in the surface treatment agent can make the adhesivity of the epithelium of possess hydrophilic property obtain long term maintenance, effectively suppresses the generation of peculiar stink in the solder flux.
The preparation method of above-mentioned polyallylamine resin is not particularly limited, and can adopt the known method preparation.Be not particularly limited as the polyallylamine resin, for example, can use " PAA-05 " (polyallylamine, weight-average molecular weight 5000, trade(brand)name, Ri Dong spin Co., Ltd.'s system), " PAA-15C " (polyallylamine, weight-average molecular weight 15000, trade(brand)name, Ri Dong spin Co., Ltd.'s system), " PAA-D11-HCl " commercially available polyallylamine resins such as (allylamine hydrochloride-diallylamine hydrochloride multipolymer, weight-average molecular weight 10000, trade(brand)name, Ri Dong spin Co., Ltd.'s system).In the scope of not damaging the object of the invention; can use methods such as utilizing acidylate that its part amino has been carried out the polyallylamine resin of modifying, with acid part or all of amino carried out neutral polyallylamine resin; in not influencing deliquescent scope, can use by linking agent and carry out crosslinked polyallylamine resin etc.
Preferably, the weight-average molecular weight of above-mentioned polyallylamine resin is in the scope of lower limit 5000, the upper limit 70000.If less than 5000, then the epithelium of possess hydrophilic property is insufficient to the absorption of polyallylamine resin, might can't obtain sufficient odor-resistant result, thereby not preferred.If surpass 70000, then the viscosity of surface treatment agent increases, and might hinder epithelium and form.Above-mentioned lower limit more preferably 10000, the above-mentioned upper limit more preferably 25000.Should illustrate that above-mentioned weight-average molecular weight is the value of measuring as the GPC method of standard according to styrene polymer.
Preferably, with solid component meter, the content of the above-mentioned polyallylamine resin in the surface treatment agent is in the scope of lower limit 100 ppm, the upper limit 5000 ppm.If less than 100 ppm then might can't obtain sufficient odor-resistant result, thereby not preferred.If surpass 5000 ppm, then the viscosity of surface treatment agent increases, and might hinder epithelium and form, and might cause the distinctive bad-smell problem of polyallylamine resin simultaneously.Above-mentioned lower limit is 300 ppm more preferably, and the above-mentioned upper limit is 1000 ppm more preferably.
The surface treatment agent that the present invention uses further contains the silicon dioxide granule by the vinyl alcohol polymer lining.Silicon dioxide granule has the hydrophilic effect of raising epithelium that obtains from its concaveconvex shape.And, by vinyl alcohol polymer is coated on silicon dioxide granule, can suppress can keep wetting ability for a long time because of silicon-dioxide exposes the stench that causes.
Be not particularly limited as above-mentioned silicon dioxide granule, for example can enumerate aerosil, colloid silica etc.Above-mentioned aerosil for example in gas phase halogenated silanes such as trichlorosilane, tetrachloro silicane (halosilane) being carried out the material that pyrohydrolysis is made, and is the big particulate of surface-area.Above-mentioned colloid silica is to make the silicon sol of sour stable form or alkali stable form be scattered in the material that forms in the water.Preferably, the median size of silicon dioxide granule is in the scope of lower limit 5nm, upper limit 100nm.Above-mentioned lower limit is 7nm more preferably, and the above-mentioned upper limit is 60nm more preferably.If the not enough 5nm of above-mentioned median size, the concavo-convex deficiency of the epithelium that then forms by surface treatment, wetting ability reduces, if surpass 100nm, then generates the agglutinator of big particle diameter in the surface treatment agent, applies the operation reduction.Should illustrate that the median size here is meant, when the cumulative volume of silicon dioxide granule was asked summation curve as 100%, this summation curve was the particle diameter of 50% point, and this median size is measured according to dynamic light scattering method.
Above-mentioned silicon dioxide granule is covered by vinyl alcohol polymer.Be not particularly limited as vinyl alcohol polymer, but preferred especially saponification deg is the vinyl alcohol polymer more than 90%.If saponification deg less than 90%, then wetting ability is poor sometimes.Saponification deg is more preferably more than 95%.Vinyl alcohol polymer can be the material that a part of modification has been carried out in carboxyl acid modified, silicon modification, amine modification, mercaptan modification etc.In addition, the polymerization degree of optimal ethylene alcohol base polymer is in the scope of lower limit 300, the upper limit 1500, more preferably in the scope of lower limit 500, the upper limit 1300.
In silicon dioxide granule by the vinyl alcohol polymer lining, the mass ratio of silicon dioxide granule and vinyl alcohol polymer (silicon dioxide granule: the vinyl alcohol polymer of lining silicon dioxide granule) in the scope of lower limit 30:70, upper limit 70:30.By making it in above-mentioned scope, thereby can effectively be covered silicon dioxide granule, suppress exposing of silicon dioxide granule.In addition, preferably, the median size of above-mentioned silicon dioxide granule by vinyl alcohol polymer lining is in the scope of lower limit 5nm, upper limit 1000nm.Mass ratio by making silicon dioxide granule and vinyl alcohol polymer and by the median size of the silicon dioxide granule of vinyl alcohol polymer lining in above-mentioned scope, can make silicon dioxide granule form good lining state, effectively suppress the generation of exposing the stink that causes because of silicon dioxide granule by the vinyl alcohol polymer lining.
Manufacture method as above-mentioned silicon dioxide granule by vinyl alcohol polymer lining is not particularly limited, and for example can be set forth in the method for dispersed silicon dioxide particle in the vinyl alcohol polymer aqueous solution etc.Wherein, when vinyl alcohol polymer was mixed with silicon dioxide granule, both were because of the interaction aggegation.By using ultrasonic dispersing machine, small medium dispersion machine (small medium Fen San Machine) to wait to force the agglutinator that disperses such aggegation to form, can prepare silicon dioxide granule by the vinyl alcohol polymer lining.Should illustrate, about dispersion machine, use the stirrer that only has stirring action, agglutinator is fully disperseed, must use the same the have machine that grinds function, the perhaps the same dispersion machine that has obvious mixing effect in small part with ultrasonic wave with shredder.As the object lesson of this dispersion machine, for example can enumerate Japanese smart mechanism and make the made ultrafine crusher (super mill) of made ultrasonic homogenizer (US シ リ ー ズ) and aboveground making (HM-15).Disperse to remove the state of aggregation of silicon dioxide granule and vinyl alcohol polymer by carrying out such pressure, form lining particle in good condition, promptly with the be covered surface of each particle of vinyl alcohol polymer.Therefore, silicon dioxide granule is in the aqueous solution, as dispersion and stable existence.
Above-mentioned surface treatment agent can contain the hydrophilic resin beyond above-mentioned polyallylamine resin and the vinyl alcohol polymer.Hydrophilic resin as such is not particularly limited, and can use well-known hydrophilic resin in the past, for example can enumerate the hydrophilic resin of the water-soluble or water dispersible that contains hydroxyl, carboxyl, amide group, amino, sulfonic group and/or ether base etc.Wherein, demonstrate the viewpoint of good hydrophilicity from the epithelium that forms by surface treatment, above-mentioned hydrophilic resin preferably polyethylene pyrrolidone, polyacrylic acid, Polystyrene Sulronate, polyacrylamide, carboxymethyl cellulose, polyethylene oxide, water-soluble nylon, the monomeric multipolymer that forms these polymkeric substance, 2-methoxy polyethylene glycol methacrylate-styrene polymer/vinylformic acid 2-hydroxyl ethyl ester multipolymer etc. have the acronal of polyoxyethylene chain etc.
These hydrophilic resins have excellent wetting ability and water-proof while, and himself is destitute of smell, and are difficult for the absorption stink substance.Therefore, by the formed epithelium of the surface treatment agent that contains these hydrophilic resins, also be difficult for deterioration even contact with water droplet or flowing water, the inorganics such as malodorous silicon-dioxide or other residual monomer composition that distribute dust smell or adsorbent are difficult for exposing the epithelium surface.Thus, can suppress treated material disperses and distributes the dust smell or corrode.
The silicon dioxide granule of above-mentioned surface treatment agent and the total content of vinyl alcohol polymer are in the scope of lower limit 0.2 quality %, the upper limit 25 quality %.If total content less than 0.2 quality %, then surface treatment agent can't obtain to make film fully, and formed epithelium can't obtain sufficient wetting ability.If total content surpasses 25 quality %, the then easy aggegation of surface treatment agent, operation and epithelium poor properties.Above-mentioned lower limit is preferably 1 quality %, and the above-mentioned upper limit is preferably 20 quality %.
The solvent of surface treatment agent of the present invention is not particularly limited, but from viewpoints such as liquid waste disposal, preferably with the solvent of water as main component.In addition, but dual-purpose is used to make making the film raising, forming the solvent of more even level and smooth epithelium of surface treatment agent.As solvent, if use in the coating commonly used can with the mixed uniformly solvent of water, be not particularly limited, for example can enumerate the organic solvent of alcohols, ketone, ester class, ethers etc.Preferably, with respect to surface treatment agent of the present invention, the usage quantity of above-mentioned solvent is in the scope of lower limit 0.01 quality %, the upper limit 5 quality %.
Surface treatment agent of the present invention can further contain other additive.Be not particularly limited as above-mentioned other additive, for example can enumerate solidifying agent, dispersion agent, rust-inhibiting additive, antiseptic-germicide, odor control additive, pigment, tensio-active agent, lubricant, reodorant etc.
Be not particularly limited as above-mentioned solidifying agent, for example can enumerate epoxy compounds, dialdehyde compounds, oxybenzene compound, carbamate compounds etc.
Be not particularly limited as above-mentioned dispersion agent, can enumerate tensio-active agent, dispersion resin etc.
Be not particularly limited as above-mentioned rust-inhibiting additive, for example can enumerate tannic acid, imidazolium compounds, triaizine compounds, triazole compounds, guanine compound, hydrazine compound, zirconium compounds etc.Wherein, owing to can effectively give rust-preventing characteristic, thereby preferred zirconium compounds.Be not particularly limited as zirconium compounds, for example can enumerate K
2ZrF
6Deng alkali metal fluosilicate zirconate, (NH
4)
2ZrF
6Deng fluozirconate, H
2ZrF
6Deng soluble fluoride zirconate such as fluorine zirconic acid etc.; Chromium fluoride; Zirconium white etc.
Be not particularly limited as above-mentioned antiseptic-germicide, for example can enumerate Zinc Pyrithione, 2-(4-thiazolyl)-benzoglyoxaline, 1,2-benzisothiazole (1,2-benzisothiazolin), 2-n-octyl-4-isothiazoline-3-ketone, N-(fluorine dichloromethane sulfenyl) phthalic imidine, N, N-dimethyl-N '-phenylol-N '-(fluorine dichloromethane sulfenyl)-sulphonamide, methyl 2-benzimidazolecarbamate, tetramethyl-thiuram disulfide, N-(trichloro-methylthio)-4-hexanaphthene-1,2-dicarboximide (dicarboximide), barium metaborate etc.To make it be concentration more than 10 ppm with respect to surface treatment agent by adding above-mentioned antiseptic-germicide, thereby can bring into play effect.
Be not particularly limited as above-mentioned odor control additive, for example can enumerate organism with amide group and/or phenylol etc.Particularly use chromate change into treatment agent the time, these odor control additives can suppress the distinctive stink of chromic salt.Therefore, change into treatment agent and change into processing, then do not need to add above-mentioned odor control additive as long as use the zirconium class to change into Chrome-free such as treatment agent.
As organism with above-mentioned amide group and/or phenylol, for example can enumerate water soluble polyamide, flavonoid, water-based phenol, hydrazine derivative (for example carbazide, adipic dihydrazide (adipyl hydrazide), sebacoyl hydrazine, dodecanedioic acid two hydrazides, isophthalic dihydrazide, 1,6-hexa-methylene-two (N, N '-dimethylamino urea), two (N, the amino 4-phenyl of N-dimethyl hydrazides) methane (1,1,1', 1'-tetramethyl-4,4'-(methylenedi-p-phenylene) disemicarbazide) etc.) etc.
As above-mentioned pigment, for example can enumerate titanium dioxide (TiO
2), zinc oxide (ZnO), zirconium white (ZrO), lime carbonate (CaCO
3), barium sulfate (BaSO
4), aluminum oxide (Al
2O
3), kaolin (kaolin clay), carbon black, ferric oxide (Fe
2O
3, Fe
3O
4), aluminum oxide (Al
2O
3) wait various tinting pigments such as mineral dye or pigment dyestuff etc.
As the preparation method of above-mentioned surface treatment agent, can enumerate the silicon dioxide granule of prepared beforehand by the vinyl alcohol polymer lining, add the hydrophilic resin aqueous solution afterwards and carry out concentration adjustment, add the method for polyallylamine resin etc. then.
As the coating method of above-mentioned surface treatment agent, can enumerate pickling process, spray method etc.
Preferably, the thickness of epithelium is that the epithelium amount is at lower limit 0.1g/m
2, the upper limit 3 g/m
2Scope in.The above-mentioned upper limit is 1 g/m more preferably
2The thickness less than 0.1 g/m of epithelium
2The time, the stink inhibition of the epithelium that obtains may be insufficient, thereby not preferred.
The surface treatment method of heat exchanger of the present invention is used for the non-aggressive solder flux soldering heat exchanger made by aluminium, easily adheres on this heat exchanger and causes malodorous solder flux.Above-mentioned non-aggressive solder flux soldering heat exchanger is to adopt non-aggressive solder flux method for brazing to come aluminium bases such as aluminium radiator fin or aluminum pipe are carried out the heat exchanger that soldering forms.As the purposes of above-mentioned non-aggressive solder flux soldering heat exchanger, for example can enumerate the used for automobile air conditioning vaporizer.
Wherein,,, then be not particularly limited, for example can enumerate No. 3000 series alloys, No. 4000 series alloys etc. so long as make by aluminium and/or aluminium alloy as aluminium base.The aluminum-made heat exchanger that adopts the surface treatment method of above-mentioned heat exchanger to obtain also is one of the present invention.
The surface treatment method of heat exchanger of the present invention had the treatment process of changing into before carrying out above-mentioned deodorization treatment process.Changing into treatment process is in order to give non-aggressive solder flux soldering heat exchanger rust-preventing characteristic, to form the operation that changes into epithelium by changing into treatment agent on the surface of this heat exchanger.From to the burden of environment and the viewpoint of giving excellent rust-preventing characteristic effect, change into the treatment agent that changes into that uses in the treatment process and preferably change into treatment agent as the zirconium class that epithelium forms composition with zirconium.
Wherein, in the past, change into when handling using chromate to change into heat exchanger that treatment agent carried out soldering, owing to formed the good epithelium that changes into, thereby can keep adhesivity between the epithelium of heat exchanger and possess hydrophilic property for a long time well by changing into epithelium.But, as mentioned above, for using the zirconium class to change under the situation of treatment agent to the misgivings of environment, sometimes can't be in soldering heat exchanger on form the good epithelium that changes into, at this moment, epithelium that can't the long term maintenance possess hydrophilic property is to the adhesivity of heat exchanger.Therefore, the epithelium of possess hydrophilic property or change into epithelium generation deterioration, heat-exchanger surface exposes, and causes remaining in the problem that solder flux on the heat-exchanger surface produces peculiar stink.
Surface treatment method according to the heat exchanger that has used surface treatment agent of the present invention, even using chromate to change under the situation of treatment agent, the adhesivity of epithelium that also can the long term maintenance possess hydrophilic property, change under the situation of treatment agent further using the zirconium class to change into Chrome-free such as treatment agent, particularly compare with hydrophilizing agent in the past, the adhesivity of the epithelium of possess hydrophilic property significantly improves and can long term maintenance.Therefore, because lining state that can the long term maintenance heat-exchanger surface, thereby can be suppressed at the distinctive stink of solder flux that produces in the non-aggressive solder flux soldering heat exchanger effectively.
Wherein, change into as the zirconium class that the supply source of above-mentioned zirconium is not particularly limited in the treatment agent, for example can enumerate K
2ZrF
6Deng alkali metal fluosilicate zirconate, (NH
4)
2ZrF
6Deng fluozirconate, H
2ZrF
6Deng soluble fluoride zirconate such as fluorine zirconic acid etc.; Chromium fluoride; Zirconium white etc.
Preferably, as concentration of metal ions, the content of zirconium is in the scope of lower limit 20ppm, the upper limit 10000 ppm in the above-mentioned zirconium class treatment agent.If not enough above-mentioned lower limit, then the performance that changes into epithelium of gained might be insufficient, if surpass the above-mentioned upper limit, then might can't expect than this better effect and uneconomical.Above-mentioned lower limit is 50 ppm more preferably, and the above-mentioned upper limit is 2000 ppm more preferably.Can in above-mentioned zirconium class treatment agent, add acid such as phosphoric acid, mangaic acid, permanganic acid, vanadic acid, wolframic acid, molybdic acid.
Preferably, the pH of above-mentioned zirconium class treatment agent is in the scope of lower limit 2.0, the upper limit 6.5.If pH less than 2.0 then might cause corroding excessive and can't form sufficient epithelium.If pH above 6.5, then might cause corroding insufficient and can't obtain good epithelium.Above-mentioned lower limit more preferably 3.0, the above-mentioned upper limit more preferably 5.5.Can use basic cpds such as acidic cpds such as nitric acid, sulfuric acid and sodium hydroxide, potassium hydroxide, ammonia to regulate pH.
Use the treatment process that changes into that above-mentioned zirconium class treatment agent carries out, be not particularly limited, can be undertaken by the coated article surface is contacted with treatment agent.Preferably, above-mentionedly change into treatment temp during the treatment process in the scope of 20 ℃ of lower limits, 80 ℃ of the upper limits.More preferably 30 ℃ of above-mentioned lower limits, more preferably 70 ℃ of the above-mentioned upper limits.Preferably, above-mentioned change into processing change into the treatment time in lower limit 5 seconds, 1200 seconds scope of the upper limit.Above-mentioned lower limit more preferably 30 seconds, the above-mentioned upper limit more preferably 120 seconds.Be not particularly limited as formation processing method, for example can enumerate pickling process, spray method etc.
Preferably, the surface treatment method of heat exchanger of the present invention has the washing treatment process above-mentioned after changing into treatment process.For adhesivity between the epithelium that does not influence and obtain in the deodorization treatment process afterwards etc., the washing treatment process after this changes into should be carried out more than 1 time or 1 time.At this moment, last washing suits to carry out with pure water.Any that can adopt spraying washing or dipping washing handled in washing after this changes into, but also these methods of dual-purpose are washed.
In the surface treatment method of heat exchanger of the present invention, carry out drying process after the washing treatment process after above-mentioned changing into, be inessential.Directly carry out the deodorization treatment process even do not carry out drying process changing under the wet state of filtering of epithelium, also can the performance that obtain not exerted an influence.In addition, under the situation of carrying out drying process, preferably carry out cold air drying, warm air drying etc.Under the situation of carrying out warm air drying,, be preferably below 300 ℃ from saving the viewpoint of heat energy.
The surface treatment method of heat exchanger of the present invention above-mentioned change into treatment process before, have the cleanup acid treatment operation.The cleanup acid treatment operation is to remove operation attached to dirts such as the solder flux on the heat exchanger, salt etc. with acid detergent.Above-mentioned acid detergent contains nitric acid and sulfuric acid, also has molysite.And this moment is dual-purpose nitric acid and sulfuric acid preferably.As acid concentration, be preferably 1 ~ 10N, more preferably 3 ~ 6N.In addition, add above-mentioned molysite, thereby have the advantage of can be more effectively removing deflux etc. by the oxytropism washing composition.
Be not particularly limited as above-mentioned molysite, for example can enumerate ferric sulfate, iron nitrate, iron acetate, iron(ic) chloride, ironic citrate, ferric fluoride, iron bromide, tertiary iron phosphate, thionamic acid iron, Ferrox, ironic lactate etc., but because low price, thereby be preferably selected from least a in ferric sulfate, iron nitrate, iron acetate and the iron(ic) chloride.Preferably, in above-mentioned acid detergent the content of molysite in the scope of lower limit 0.01 quality %, the upper limit 5 quality %.By the content that makes molysite is in the above-mentioned scope, can more effectively remove deflux etc.Above-mentioned lower limit is 0.1 quality % more preferably, and the above-mentioned upper limit is 1 quality % more preferably.
The pH of above-mentioned acid detergent is preferably below 4.By making pH is below 4, can obtain good washing effect.
Can adopt spray method, pickling process etc. in the past known method carry out above-mentioned cleanup acid treatment operation.Preferably, in being the scope of 10 ℃ of lower limits, 85 ℃ of the upper limits, the liquid temperature of above-mentioned acid detergent carries out the cleanup acid treatment operation.In addition, preferably, the treatment time is in lower limit 30 seconds, 5 minutes scope of the upper limit.If 10 ℃ of liquid temperature less thaies or treatment time less than 30 seconds, then the removal of segregation thing etc. is insufficient sometimes, if the liquid temperature surpasses 85 ℃ or surpass 5 minutes, it is excessive then might to cause corroding.
[embodiment]
Below, enumerate embodiment and comparative example is described in further detail the present invention.The present invention is not only limited to these embodiment.In addition, in an embodiment, if no special instructions, " % " expression " quality % ", if no special instructions, " part " expression " mass parts ".
Embodiment 1
The preparation of＜surface treatment agent＞
Vinyl alcohol polymer (saponification deg is more than 98%) powder 25 mass parts are dissolved in pure water 950 mass parts make the aqueous solution, in this aqueous solution, add aerosil (median size is 40nm) 25 mass parts, stir, form agglutinator.Then, use ultrasonic dispersing machine (Japanese smart mechanism is made made ultrasonic homogenizer) to force to disperse this agglutinator, obtaining median size is the dispersion liquid of the vinyl alcohol polymer lining silicon dioxide granule of 500nm.Further in the aqueous solution, add Zinc Pyrithione as antiseptic-germicide, make its concentration reach 10ppm, " PAA-15C " (polyallylamine, weight-average molecular weight 15000, trade(brand)name, Ri Dong spin Co., Ltd.'s system) of adding 500ppm again as the polyallylamine resin, obtains surface treatment agent.Should illustrate, after with deionized water a part of surface treatment agent that obtains being diluted, measure machine (" ELS-800 ", trade(brand)name, big mound electronics society system) by dynamic light scattering and measure median size.
Use contains the acid detergent of nitric acid 10 quality %, sulfuric acid 5 quality %, iron 1 quality %, in this acid detergent being warming up to 65 ℃ bath, (trade(brand)name, Japanese テ ス ト パ ネ Le society system, 70mm * 150mm * 0.8mm) and clear and electrician's manufacture-illegal corrosive flux soldering system used for automobile air conditioning vaporizer (NB vaporizer) dipping 4 minutes, it is fully clean with tap water to propose the back with " 5000 series aluminum ".Then, changing into treatment agent (" ア ル サ ー Off 90 ", trade(brand)name, Japan paint society system) in the zirconium class that will change into treatment agent as Chrome-free is warming up in 50 ℃ the bath, said sample and used for automobile air conditioning vaporizer were flooded 90 seconds, fully clean with tap water afterwards.
Then this sample and used for automobile air conditioning vaporizer being placed 20 ℃ the bath dipping 1 minute of above-mentioned surface treatment agent, after the proposition, is under 170 ℃ the temperature arriving temperature, heat drying 45 minutes, and making the epithelium amount is 1g/m
2Deodorization handle sample and deodorization is handled the used for automobile air conditioning vaporizer.
Embodiment 2
The use level of polyallylamine is changed to 1000ppm, in addition, adopt the method identical to make deodorization and handle sample and deodorization processing used for automobile air conditioning vaporizer with embodiment 1.
Embodiment 3
The use level of polyallylamine is changed to 5000ppm, in addition, adopt the method identical to make deodorization and handle sample and deodorization processing used for automobile air conditioning vaporizer with embodiment 1.
Comparative example 1
Except not adding polyallylamine, adopt the method identical to make deodorization and handle sample and deodorization processing used for automobile air conditioning vaporizer with embodiment 1.
Comparative example 2
Cooperate " PVAM0595B " (polyvinylamine, weight-average molecular weight 60000, trade(brand)name, Mitsubishi Chemical society system) of 1000ppm to replace polyallylamine as having amino resin, in addition, adopt the method identical to make deodorization and handle sample and deodorization processing used for automobile air conditioning vaporizer with embodiment 1.
Comparative example 3
Cooperate the glycine of 1000ppm to replace polyallylamine, in addition, adopt the method identical to make deodorization and handle sample and deodorization processing used for automobile air conditioning vaporizer with embodiment 1.
Comparative example 4
Cooperate the phenol of 1000ppm to replace polyallylamine, employed odor control additive when this phenol changes into treatment agent for using chromate in addition, adopts the method identical with embodiment 1 to make deodorization and handles sample and deodorization processing used for automobile air conditioning vaporizer.
Comparative example 5
Cooperate the 1000ppm adipic dihydrazide to replace polyallylamine, employed odor control additive when this adipic dihydrazide changes into treatment agent for using chromate, in addition, adopt the method identical to make deodorization and handle sample and deodorization processing used for automobile air conditioning vaporizer with embodiment 1.
Reference example 1
Adopt the method identical to make deodorization processing sample with comparative example 1, and use the clear and electrician who makes by the vacuum brazing method to make used for automobile air conditioning vaporizer (VB vaporizer) and replace clear and electrician's manufacture-illegal corrosive flux soldering system used for automobile air conditioning vaporizer (NB vaporizer), in addition, adopt the method identical to make deodorization processing used for automobile air conditioning vaporizer with comparative example 2.
＜adhesivity＞
Respectively the deodorization that obtains is handled the primary product of sample and at room temperature impregnated in 1 week in the pure water and deterioration deodorization handle sample and stick cellophane tape (ニ チ バ Application system) and peel off.Measure residual epithelium area, estimate according to following benchmark.The result is as shown in table 1:
Peel off at zero: 0%
△: peel off below 50%
*: 50 ~ 100% peel off.
＜wetting ability＞
Respectively the deodorization that obtains is handled the primary product of sample and at room temperature impregnated in 1 week in the pure water and deterioration the hydrophilization sample stick adhesive tape and peel off.The pure water that drips 2 μ l on this adhesive tape stripping portion is measured contact angle.Carry out measurement of contact angle by automatic contact angle instrument (from Move contact angle Meter) " CA-Z " (consonance come to the surface length of schooling).Should illustrate, about hydrophilic evaluation, be qualified below 30 °.
＜stink＞
Adopt to hear smelly method respectively to the primary product of used for automobile air conditioning vaporizer and in water dipping 168 hours and deterioration the used for automobile air conditioning vaporizer carried out for 5 stages and estimate.Should illustrate, about the evaluation of stink, be qualified below 2 minutes:
0 minute ... odorless
1 minute ... smell slight stink reluctantly
2 minutes ... smell an offensive odor like a cork
3 minutes ... smell an offensive odor significantly
4 minutes ... smell the intensive stink
5 minutes ... smell very intensive stink.
Above result is as shown in table 2.
As shown in Table 1, since adopt used for automobile air conditioning vaporizer that the surface treatment method of heat exchanger of the present invention handles can the long term maintenance heat exchanger and the epithelium of possess hydrophilic property between adhesivity, and the deterioration that can suppress the epithelium of possess hydrophilic property and change into epithelium, thereby distinctive stink in the solder flux that remains in heat-exchanger surface demonstrated excellent stink inhibition.
In addition, comparative example 1 and reference example 1 are compared as can be known, though the heat exchanger that adopts the vacuum brazing method to make existed the problem of stink inhibition difference in the past, to compare degree lower with the stink inhibition problem of non-aggressive solder flux soldering heat exchanger.In addition, owing to remain in the solder flux possess hydrophilic property on the surface of non-aggressive solder flux soldering system used for automobile air conditioning vaporizer, even therefore the epithelium of possess hydrophilic property is peeled off, its wetting ability is also good in the used for automobile air conditioning vaporizer of making according to the vacuum brazing method.But,, because in comparative example 1, cause the distinctive stink of solder flux because of the residual substrate that the aluminium of solder flux arranged exposes, thereby think that the stink inhibition in the comparative example 1 is poorer than reference example 1 even in this case.When on the heat exchanger of such non-aggressive solder flux soldering system, handling,, also can make the heat exchanger of the good stink inhibition of long-term maintenance if adopt the surface treatment method of heat exchanger of the present invention.
[utilizability on the industry]
The surface treatment method of heat exchanger of the present invention, contain nitric acid and sulfuric acid by making, contact with the non-aggressive solder flux soldering heat exchanger of being made by aluminium with the acid detergent of the molysite of specified quantitative, when making then the zirconium class change into inorganic agent to contact with above-mentioned heat exchanger, make the silicon dioxide granule that contains by the vinyl alcohol polymer coating, and polyallylamine resin and vinyl alcohol polymer contact with above-mentioned heat exchanger for the surface conditioning agent of being decided in the scope with total content and the mass ratio of silicon dioxide granule, thereby can the long term maintenance heat exchanger and have adhesiveness between hydrophilic epithelium, thereby form distinctive stink in the solder flux that remains in heat-exchanger surface is had good stink inhibition and the method for hydrophilic epithelium. According to the present invention, even on the non-aggressive solder flux soldering heat exchanger of residual flux, also can effectively form and keep epithelium, suppress special cacodorous generation in the solder flux.
Claims (5)
1. the surface treatment method of a heat exchanger, it comprises:
Make the non-aggressive solder flux soldering heat exchanger that acid detergent contact made by aluminium cleanup acid treatment operation (1),
Make the zirconium class change into described aluminium after the treatment agent contact pickling treatment process change into treatment process (2) and
Make surface treatment agent contact change into the deodorization treatment process (3) of the described aluminium after the treatment process; It is characterized in that:
Described acid detergent contains nitric acid and sulfuric acid, and contains the molysite of 0.01 ~ 5 quality %;
Described surface treatment agent contains silicon dioxide granule and the polyallylamine resin by the vinyl alcohol polymer lining, the described silicon dioxide granule that is contained in the described surface treatment agent and the total content of described vinyl alcohol polymer are 0.2 ~ 25 quality %, and the mass ratio of described silicon dioxide granule and described vinyl alcohol polymer is 30:70 ~ 70:30.
2. the surface treatment method of heat exchanger as claimed in claim 1, wherein, described molysite is selected from least a in ferric sulfate, iron nitrate, iron acetate and the iron(ic) chloride.
3. the surface treatment method of heat exchanger as claimed in claim 1, wherein, described non-aggressive solder flux soldering heat exchanger is the used for automobile air conditioning vaporizer.
4. surface treatment agent that is used for the surface treatment method of claim 1,2 or 3 described heat exchangers.
A surface treatment method that adopts claim 1,2 or 3 described heat exchangers and aluminum-made heat exchanger.
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|---|---|---|---|
| JP2010014777A JP2011153745A (en) | 2010-01-26 | 2010-01-26 | Surface treatment method for heat exchanger, surface treatment agent and aluminum heat exchanger |
| JP2010-014777 | 2010-01-26 |
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| CN103721965A (en) * | 2013-11-25 | 2014-04-16 | 青岛盛嘉信息科技有限公司 | Treatment process of aluminium alloy after brazing |
| CN107513705A (en) * | 2017-08-11 | 2017-12-26 | 江苏富翔汽车科技有限公司 | A kind of high anti-corrosion automobile fitting finished surface handling process metal treatment fluid |
| CN108355936A (en) * | 2018-02-02 | 2018-08-03 | 上海旺烨静电喷涂技术有限公司 | A kind of evaporator for air-conditioning system of automobile external coating technique |
| CN110832122A (en) * | 2017-09-19 | 2020-02-21 | 奥野制药工业株式会社 | Surface treatment agent for dyed aluminum or aluminum alloy anodic oxide coating, and surface treatment method, sealing method, and article using same |
| CN114008244A (en) * | 2019-06-26 | 2022-02-01 | 马勒国际有限公司 | Method for passivating aluminum surfaces with solder |
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| EP3233732B8 (en) * | 2014-12-19 | 2020-06-17 | DDP Specialty Electronic Materials US 9, LLC | Process for preparing monohydrogentrihalosilanes |
| CN105440311B (en) * | 2016-01-07 | 2018-02-27 | 深圳先进技术研究院 | The surface treatment method and epoxy resin composite material of silica filler, silica filler |
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| CN110832122A (en) * | 2017-09-19 | 2020-02-21 | 奥野制药工业株式会社 | Surface treatment agent for dyed aluminum or aluminum alloy anodic oxide coating, and surface treatment method, sealing method, and article using same |
| CN110832122B (en) * | 2017-09-19 | 2021-05-11 | 奥野制药工业株式会社 | Surface treatment agent for dyed aluminum or aluminum alloy anodic oxide coating, and surface treatment method, sealing method, and article using same |
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| CN114008244A (en) * | 2019-06-26 | 2022-02-01 | 马勒国际有限公司 | Method for passivating aluminum surfaces with solder |
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| JP2011153745A (en) | 2011-08-11 |
| US8815022B2 (en) | 2014-08-26 |
| CN102134720B (en) | 2014-01-01 |
| US20110180249A1 (en) | 2011-07-28 |
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Address after: Japan Osaka lake north of Osaka north 2 chome 1 No. 2 Patentee after: NIPPON PAINT HOLDINGS CO.,LTD. Patentee after: SHOWA DENKO Kabushiki Kaisha Address before: Japan Osaka lake north of Osaka north 2 chome 1 No. 2 Patentee before: NIPPON PAINT Co.,Ltd. Patentee before: SHOWA DENKO Kabushiki Kaisha |
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Address after: Japan Tokyo Shinagawa District South Shinagawa 4 chome 1 No. 15 Patentee after: NIPPON PAINT SURF CHEMICALS CO.,LTD. Patentee after: Mahlebeier cooling and heating system (Japan) Co.,Ltd. Address before: Japan Tokyo Shinagawa District South Shinagawa 4 chome 1 No. 15 Patentee before: NIPPON PAINT SURF CHEMICALS CO.,LTD. Patentee before: SHOWA DENKO Kabushiki Kaisha |
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